Hydrosilation of fluorinated olefins with cobalt catalysts

ABSTRACT

Alpha-fluorinated olefins are hydrosilated using selected cobalt compounds as catalysts. The products are useful in coatings, and as chemical intermediates, elastomers, and caulks.

BACKGROUND OF INVENTION

This invention concerns a process for the hydrosilation of alpha-fluorinated olefins, in which selected cobalt compounds are used as catalysts.

The hydrosilation of olefins is a powerful and versatile method for the synthesis of various silicon compounds. Hydrosilation reactions using various silicon hydride and olefin combinations are known to be catalyzed by a variety of selected metal compounds, and in particular certain of the Group VIII metals have been found to be especially useful.

The hydrosilation of alpha-fluorinated olefins has been carried out using several Group VIII metal compounds [see for example I. Ojima, et al., J. Organometal. Chem., vol. 260, p. 335-346 (1984)].

However, in many of these reactions relatively poor yields of the simple hydrosilation product and/or relatively large amounts of other byproducts are obtained. It is believed that the highly electron withdrawing nature of the fluorine atom makes hydrosilation of alpha-fluorinated olefins difficult.

Cobalt compounds are known to effect hydrosilation of simple (unfluorinated) olefins, see for example J. F. Harrod and A. J. Chalk, J. Am. Chem. Soc., vol. 87, p. 1133 (1965). However, the hydrosilation of alphafluorinated olefins using cobalt compounds was not reported.

SUMMARY OF THE INVENTION

This invention concerns a process for the hydrosilation of alpha-fluorinated olefins, comprising, contacting a silicon hydride with an olefin of the formula H₂ C═CHCFR¹ R² and a catalytically effective amount of catalyst of the formula Co₂ (CO)_(8-z) L_(z), wherein:

R¹ is fluorine or perfluorohydrocarbyl;

R² is fluorine, hydrogen, hydrocarbyl, or substituted hydrocarbyl;

z is 0 or an integer of 1 to 7;

each L is independently CO, PR³ ₃ or P(OR⁴)₃ ;

R³ is hydrocarbyl;

R⁴ is hydrocarbyl; and provided that when L is PR³ ₃, only one or two of R³ is aryl.

DETAILS OF THE INVENTION The basic hydrosilation reaction which the process accomplishes may typically be represented by the equation ##STR1##

The olefins used in the instant process are fluorinated in the alpha position, that is, there is at least one fluorine atom attached to the carbon atom bound to a vinylic carbon atom. In preferred olefins, R¹ is perfluoroalkyl and R² is fluorine. In especially preferred olefins, R¹ is perfluoro-n-alkyl containing 2 to 20 carbon atoms and R2 is fluorine. In another preferred olefin, R² is ω-hydro or ω-haloperfluoro-n-alkyl, and R¹ is fluorine. Herein "halo" means chloro, bromo, or iodo. By the term "hydrocarbyl" herein is meant a univalent radical containing carbon and hydrogen. By the term "substituted hydrocarbyl" herein is meant a hydrocarbyl radical containing substituents that, with the exception of olefinic and acetylenic bonds, are not reactive under process conditions, and do not interfere with the process. Olefinic and acetylenic bonds present in hydrocarbyl groups may themselves be isomerized and/or hydrosilated during the process. This is desirable in some cases, for example the use of an olefin of the formula CH₂ =CH(CF₂)_(b) CH═CH₂, where b is 2 to 20, where one or both olefinic groups are hydrosilated in the process. Suitable substituents include, but are not limited to, fluoro, chloro, bromo, iodo, ether (between hydrocarbyl groups), silyl substituted alkyl (which may itself have a silicon hydride group), and silyl substituted aryl (which itself may have a silicon hydride group). Substituents that contain active hydrogen, such as hydroxy and primary amino, should be avoided.

The cobalt catalysts of the invention are carbonyl complexes. In preferred catalysts z is 0 or 2. It is preferred if each R³ and R⁴ is independently alkyl containing 1 to 6 carbon atoms, or phenyl, and especially preferred if each R³ and R⁴ is independently phenyl or methyl. The cobalt compounds are available commercially or can be made by procedures described in A. R. Manning, J. Chem. Soc. (A), p. 1135 (1968).

Another necessary process ingredient is a silicon hydride. By a "silicon hydride" is meant a compound that contains one or more hydrogen atoms bound directly to silicon (.tbd.i--H). The silicon hydride may have only to silicon one hydrogen atom bound to a silicon atom, may have more than one hydrogen bound to any particular silicon atom, and/or may have more than one silicon atom that has hydrogen bound to it. Any other group that is substantially stable during the process may be bound to the silicon, such as hydrocarbyl, including alkyl, aryl, and cycloalkyl, substituted hydrocarbyl, chloro, bromo, fluoro, alkoxy, aryloxy, acyloxy, and oxysilyl (to form a siloxane group). Many such compounds are commercially available.

One preferred silicon hydride is R⁵ nSiH_(4-n) wherein each R⁵ is independently alkyl containing 1 to 20 carbon atoms, aryl, chloro, bromo, alkoxy containing 1 to 4 carbon atoms, and acyloxy containing 1 to 6 carbon atoms, and n is 1, 2 or 3. In an especially preferred silicon hydride, each R⁵ is independently methyl, ethyl, phenyl, methoxy, ethoxy, or chloro. Another preferred silicon hydride is R⁵ _(m) H_(3-m) SiOSiR⁵ _(m) H_(3-m) wherein R⁵ is as defined above and m is 0, 1, or 2. Especially preferred R⁵ are as given above. Another preferred silicon hydride is a cyclic siloxane of the formula (R⁵ ₂ SiO)x(R⁵ _(t) H_(2-t) SiO)_(y), wherein R⁵ is as defined above, x +y is 3, 4, or 5, y is an integer of one or more, x is 0, 1, 2, 3 or 4, and t is 0 or 1. Especially preferred R⁵ groups are as defined above. Another preferred silicon hydride is a linear polysiloxane of the formula R⁵ ₃ SiO(R⁵ ₂ SiO)q(R⁵ _(s) H_(2-s) SiO)_(r) SiR⁵ ₃, wherein R⁵ is as defined above, q is 0 or an integer of 1 or more, r is an integer of 1 or more, and each s is independently 0 or 1. Especially preferred R5 groups are as given above. In preferred linear polysiloxanes q r is about 5 to about 10,000, and it is more preferred if q+r is about 10 to about 1,000. For the linear polysiloxanes, it is more preferred if each R5 is methyl, ethyl or phenyl, and most preferred if each R5 is methyl. The linear polysiloxanes which are the products of the process have the formula R⁵ ₃ SiO(R⁵ ₂ SiO)₁ [R⁵ _(s) H_(u) Si (CH₂ CH₂ CFR¹ R²)_(t) O]_(r) SiR.sup. 5₃, wherein R¹, R², R⁵, q, r, and s are as defined as above, each t is independently 1 or 2, each u is independently 0 or 1, and s +t +u for any individual silicon atom is 2.

The process is carried out at a temperature of about 0° C. to about 200° C., preferably 20° C. to 60° C. Typical reaction times are about 1 hr to about 5 days. In order to prevent decomposition of starting materials and/or products it is preferred to carry out the process in the absence of water and oxygen, so it is convenient to use an inert atmosphere above the reaction, such as nitrogen. To bring the ingredients into contact with one another it is preferred if the reaction is agitated. Products can be isolated by known techniques, depending on the properties of the products, such as evaporation of solvent, distillation or filtration. Solvents may optionally be used in the process, so long as they don't react with any of the starting materials or products. Solvents should not have any active hydrogen atoms. When all of the Si-H groups in the silane are to be reacted, it has been found advantageous to use an excess of moles of alpha-fluorinated olefin to equivalents of silicon hydride (.tbd.i--H). Thus it is preferred if the ratio of moles of olefin to equivalents of silicon hydride is about 3:1 to about 1:3, and especially preferred if it is about 1.3:1 to about 1:1. The process also requires that a catalytically effective amount of the cobalt catalyst be present. A typically effective ratio of moles of cobalt catalyst to equivalents of silicon hydride is about 0.1:1 to about 0.0001:1, preferably 0.03:1 to 0.005:1, more preferably 0.01:1 to 0.005:1.

The hydrosilated low molecular weight products of the instant process are useful as monomers for polymerization and as chemical intermediates. The hydrosilated polymers are useful as lubricants, surface modifiers, chemically and solvent resistant elastomers and caulks, and for solvent resistant coatings.

The following materials are used in the Examples: Darco® G-60 - Activated carbon available from EM Science, Gibbstown, NJ, USA.

Freon® 113 -1,1,2-trichloro-1,2,2-trifluoroethane, available from E. I. du Pont de Nemours & Co., Wilmington, DE USA

(Perfluoro-n-butyl)ethylene - Available as Zonyl® PFBE from DuPont

Trimethylsiloxy terminated polymethylsiloxanes were obtained from Huls America, Inc., Piscataway, NJ, USA

EXAMPLES Example 1

reaction of F(CF₂)₄ CH═CH₂ with Me₃ SiO(SIMEHO)₁₄ SiMe₃ and Co₂ (CO)₆ [P(OMe)₃ ]₂ Catalyst.

P(OMe)₃ (0.21 g, 0.169 mmol) and Co₂ (CO₈ (0.030 g, 0.088 mmol) were stirred in 1 ml toluene (dried and distilled from CaH₂) for 30-45 min. in a drybox. Polyhydromethylsiloxane (2 ml, 0.033 mole SiH) and F(CF₂)₄ CH═CH₂ (10 ml, 0.057 mole) were added to the catalyst solution and stirring continued for a few days. Small samples (˜0.5 ml) were occasionally withdrawn, diluted with F-113, filtered through neutral Al₂ O₃ and Darco G-60 and subjected to ¹ H NMR analysis to determine extent of the reaction. After 5 days at room temperature the reaction system was diluted with 30 ml F-113, filtered through neutral Al₂ O₃ and Darco G-60, volatiles were stripped on a rotary evaporator and under high vacuum. Yield: 4.0 g (40%) blue, transparent, viscous oil. ¹ H NMR (F-113+CDCl₃):δ 0.1-0.3 (m, SiCH₃), 0.88 (m, SiCH₂ -CH₂ -CF₂, 84% relative to Si--CH₃), 2.14 (m, SiCH₂ --CH₂ --CF₂), 4.83 (s, SiH, 13% relative to Si--CH₃); ¹⁹ FNMR (Freon® 113, CDCl₃ and Freon®11): --81.0 (t, 3F), -116.9 (m, 2F), --124.7 (m, 2F), --126.6 (m, 2F); ₂₉ Si NMR: 10.2 (m, OSI(CH₃)₃), -19.2 to -22.7 (m, OCH₃ SiCH₂ CH₂ (CF₂)₄ FO), -34.9 to -35.8 (OCH₃ SiHO). Anal. found (calcd for Me₃ SiO[SiMeCH₂ CH₂ (CF₂)₄ FO]₁₅ SiMe₃): C, 27.00 (28.26); H, 2.61 (2.63), F, 53.72 (54.20), Si, 10.47 (10.14).

EXAMPLE 2

Reaction of F(CF₂)₄ CH═CH₂ with Me₃ SiO(SiMeHO)₁₄ SiMe₃ and Co₂ (CO)₈ Catalyst.

A mixture of Co₂ (CO)₈ (6g, 17.6 mmole), polymethylhydrosiloxane (60 ml, 1.0 mole SiH) and F(CF₂)₄ --CH═CH₂ (210 ml, 1.2 mole) in a drybox was stirred for 5 days at room temperature. The reaction system was washed several times with MeOH, the bottom layer was separated, diluted with Freon® 113, filtered through neutral Al₂ O₃, silica and Darco G-60, volatiles stripped on a rotary evaporator and under high vacuum. Yield: 190g (64%), viscous, pinkish oil. ¹ H NMR (F-113 +CDC13): δ0.1-0.4 (m, SiCH₃), 0.9 (m, Si--CH₂ --CF₂ --CF₂, 69% relative to Si--CH₃); 2.2 (m, SiL CH₂ --CH₂ ---CF₂), 3.55 (s, Si-OCH₃), 4.85 (s, Si-H); ¹⁹ F NMR (THF-d₈ +F-11):-81.7 (t, 3F), -114 to -115 (br, minor), -116.5 (m, 2F), -124.3 (m, 2F), -126.3 (m, ² F); ²⁹ Si NMR (F-113+CDC13):10.2 (m, OSi(CH3)3), -21.6 (m, OCH₃ SiCH2CH2(CF2)4FO), -35.1 (m, OCH₃ SiHO), -56 to -67 (broad, minor); GPC (THF): Mn=3,480, M_(w) /M_(n) =1.33 (vs PS).

EXAMPLE 3

Preparation of Me₃ SiO(SiMeCH₂ CH₂ C₄ F₉ O)_(m)

(SiMeC₁₅ H₃₁ O)_(n) SiMe₃ (m+n=14).

A mixture of Co₂ (CO)₈ (16.5q, 48.8 mmol), polymethylhydrosiloxane (250 ml, 4.0 mole SiH), H(CH₂)₁₂ -14CH═CH₂ (165 ml, 0.6 mole) and C₄ F₉ CH═CH₂ (610 ml, 3.5 mole) under nitrogen was stirred at 55° C. for 8 days. The reaction system was worked up according to the procedure described in Example 2. Yield: 750g (61%), transparent pinkish oil, viscosity: 1,290 cSt (100° F.). 130 cSt (210° F.); ¹ H NMR (F-113+CDCl₃): δ0.2 (m, SiCH₃), 0.65 (m, Si--CH₂ --CH₂ --CH₂, (8.6% relative to Si--CH₃)), 0.8--1.0 (m, Si--CH₂ --CH₂ --CF₂ (80% relative to SiCH₃) and CH₂ CH₃), 1.4 (m, CH₂ --CH₂ --CH₂), 2.0 (m, SiCH₂ CH₂ CF₂).

EXAMPLE 4

Preparation of --[--(CH₂)₂ --(CF₂)₄ --(CH₂)--(SiMe₂ O)₂ SiMe₂ --]_(x)

A mixture of Co₂ (CO)₈ (0.1 g, 0.29 mmol), HSiMe₂ OSiMe₂ OSiMe₂ H (3.9 ml, 15.4 mmol), and CH₂ ═CH--(CF₂)₄ --CH═CH₂ (3 ml, 16.4 mmol) in a drybox was stirred at rt for 4 days then heated at 60° C. for additional 10 h. Yield: 6g (81%), dark, very viscous oil. GPC (THF):M_(n) =6,560, M_(w) /M_(n) =1.71 (vs. PS), ¹ H NMR (THF-d₈): δ0.1--0.3 (m, Si--CH₃), 0.9 (m, Si--CH₂ --CH₂ --CF₂, 85% relative to Si--CH₃), 2.2 (m. Si--CH₂ --CH₂ --CF₂).

EXAMPLE 5

Preparation of (C₈ F₁₇ CH₂ CH₂)₂ Si(CH₃)Ph.

A mixture of H₂ SiMePh (0.6 ml, 4.37 mmol), C₈ F₁₇ --CH═CH2 (3 ml, 11.1 mmol), Co₂ (CO)₈ (0.2 g, 0.58 mmol) and 0.3 ml decane (GC standard) in a drybox was stirred at rt for 24 hrs. The mixture was diluted with F-113, filtered through neutral Al₂ O₃ and Darco G-60, volatiles stripped on a rotary evaporator and under high vacuum. Yield: 3 g (68%), clear oil. ¹ H NMR (F-113+CDCl₃): δ0.2 (s, 3H), 0.9 (m, 4H), 1.9 (m, 4H), 7.2 (m, 5H); ¹⁹ F NMR (F-113+CDCl₃ +F-11): -81.2 (t, 3F), -115.7 (m, 2F), -121.7 (m, 6F), -122.6 (m, 2F), -123.0 (m, 2F), -126.2 (m, 2F); MS [M+F]: Calc: 1033.0462, Found: 1033.0272.

EXAMPLE 6

Preparation of C₆ H₁₃ SiH(CH₂ CH₂ C₄ F₉)₂

A mixture of Co₂ (CO)₈ (0.2 g, 0.58 mmol), C₄ F₉ CH═CH₂ (4 ml, 22.7 mmol) and C₆ H₁₃ SiH₃ (1 ml, 6.19 mmol) was stirred in a drybox. Progress of the reaction was followed by GC. After 48 hrs. more Co₂ (CO)₈ (0.2 g, 0.58 mmol) was added. After another 24 hrs. GC showed 78% of the desired product. The mixture was diluted with F-113, filtered through neutral Al₂ O₃ and Darco G-60, volatiles stripped on a rotary evaporator and under high vacuum. Yield: 1.5 g (39%), brown solid, T_(M) =24° C. (DSC). ¹ H NMR: δ0.7 (m, 6H), 0.9 (t, 3H), 1.3 (m, 8H), 2.1 (m, 4H), 3.8 (m, 1H); MS [M+F]: Calc. 627.1187: Found 627.1118.

EXAMPLE 7

Preparation of PhSiH(CH₂ CH₂ C₄ F₉)₂

A mixture of Co₂ (CO)₈ (0.2g, 0.58 mmol), C₄ F₉ CH═CH₂ (4 ml, 22.7 mmol), PhSiH₃ (0.8 ml, 6.43 mmol) and F-113 (2.5 ml) was stirred in a drybox. After 3 days GC showed ˜85% of the desired product. The reaction mixture was worked up according to the procedure described in Example 6. Yield: 2.5 g (65%), waxy solid, T_(M) =17° C. (DSC). ¹ H NMR (THF-d₈): δ1.2 (m, 4H), 2.2 (m, 4H), 4.6 (brs, 1H), 7.4 (m, 3H), 7.6 (m, 2H).

EXAMPLE 8

Preparation of Ph₂ SiHCH₂ CH₂ C₈ F₁₇

A mixture of h₂ SiH₂ (0.75 ml, 4.08 mmol), C₈ F₁₇ -CH.sub.═CH₂ (3 ml, 11.1 mmol), Co₂ (CO)₈ (0.1 g, 0.29 mmol) and 0.3 ml decane (GC standard) was stirred in a drybox. After 1.5 hrs. GC showed 92% of the desired product. The reaction mixture was worked up according to the procedure described in Example 6. The product was partially transformed into Ph₂ Si (OCH₃)CH₂ CH₂ C₈ F₁₇ when dissolved in MeOH during work up. Yield: 1.2 g (48%), brown oil. ¹ H NMR (F-113+CDC13): δ0.9 (m, 2H), 2.2 (m, 2H), 4.9 (brs, 1H), 7.4 (m, 3H), 7.6 (m, 2H); MS [M+F]: Calc. 649.0656, Found 649,0606.

EXAMPLES 9-17

Hydrosilylation of F(CF₂)₄ CH═CH₂ with Me₃ SiO(SiMeHO)₁₄ SiMe₃ in the presence of Co₂ (CO)₆ (PX₃)₂ ^(a)

    __________________________________________________________________________                                        Yield of                                         Catalyst        Time                                                                               Temp                                                                               SiH Conv..sup.b                                                                      .tbd.SiCH.sub.2 CH.sub.2 (CF.sub.2).sub                                        .4 F.sup.b                                  Example                                                                             Co.sub.2 (CO).sub.6 (PX.sub.3).sub.2                                                    (mol/LX10.sup.3)                                                                      (h) (°C.)                                                                       (%)   (%)                                         __________________________________________________________________________      9   P(n-Bu).sub.3                                                                           (3.90) 144 RT  75    67                                                        (7.80) 144 60  100   75                                          10   PEt.sub.3                                                                               (3.48) 120 RT  89    69                                                        (6.96)  72 60  100   74                                          11   PPh.sub.2 Me                                                                            (4.64) 120 RT  89    72                                                        (9.28) 168 60  100   79                                          12   PMe.sub.2 Ph                                                                            (4.65)  66 RT  16     7                                          13.sup.c                                                                            PMe.sub.3                                                                               (4.65)  66 RT  72    58                                          14   P(OPh).sub.3                                                                            (5.32)  48 RT  20    16                                          15   P(O-i-Pr).sub.3                                                                         (4.66) 120 RT  92    81                                          16   P(OMe).sub.3                                                                            (3.58) 120 RT  94    86                                          17   P(OMe).sub.3                                                                            (3.58)  19 60  38    32                                                                44 60  40    34                                          __________________________________________________________________________      .sup.a F(CF.sub.2)═CH.sub.2 (4.14 mol/L), Me.sub.3 SiO(SiMeHO).sub.14      SiMe.sub.3 (3.03 SiH mol/L) in toluene.                                        .sup.b Concentrations of SiH and SiCH.sub.2 CH.sub.2 (CF.sub.2).sub.4 F        determined by .sup.1 H NMR relative to Si--CH.sub.3.                           .sup.c In tetrahydrofuran.                                               

EXAMPLE 18

Reaction of F(CF₂)_(n) CH═CH₂, where n═6, 8, 10, 12 with Me₃ SiO(SiMeHO)₇₅ SiMe₃ and Co₂ (CO₈ Catalyst.

A mixture of Co₂ (CO)₈ (6 g, 17.6 mmol), polymethylhydroxiloxane (70 ml, 1.1 mole SiH), F(CF₂)_(n) CH═CH₂ (350 ml, 1.3 mole) and F-113 (475 ml) in a drybox was stirred at rt for 24 hrs. The reaction mixture was worked up according to the procedure described in Example 2. Yield: 489 g (82%), white solid, T_(M) =40° C. (DSC). ¹ H NMR (F-113+CDCl₃): δ0.1-0.3 (m, SiCH₃),0.9 (m, SiCH₂ CH₂ CF₂, 71% relative to SiCH₃), 2.2 (m, SiCH₂ CH₂ CF₂), 3.6 (s, SiOCH₃, 5.5% relative to SiCH₃), 4.9 (s, SiH, 12% relative to SiCH₃). 

What is claimed is:
 1. A process for the hydrosilation of alpha-fluorinated olefins, comprising, contacting a silicon hydride with an olefin of the formula H₂ C═CHCFR¹ R² and a catalytically effective amount of catalyst of the formula Co2(CO)_(8-z) L_(z), wherein:R¹ is fluorine or perfluorohydrocarbyl; R² is fluorine, hydrogen, hydrocarbyl, or substituted hydrocarbyl; z is 0 or an integer of 1 to 7; each L is independently CO, PR³ 3 or P(OR⁴)₃ ; R³ is hydrocarbyl; R⁴ is hydrocarbyl; and provided that when L is PR₃ 3 only one or two of R³ is aryl.
 2. The process as recited in claim wherein R¹ is perfluoroalkyl and R² is fluorine.
 3. The process as recited in claim 2 wherein R¹ is perfluoro-n-alkyl containing 2 to 20 carbon atoms and R² is fluorine.
 4. The process as recited in claim 1 wherein R² is -hydro or -haloperfluoro-n-alkyl, and R¹ is fluorine.
 5. The process as recited in claim 1 wherein z is 0 or
 2. 6. The process as recited in claim 1 wherein each R³ and each R⁴ is independently alkyl containing 1 to 6 carbon atoms, or phenyl.
 7. The process as recited in claim 6 wherein each R³ and each R⁴ is independently phenyl or methyl.
 8. The process as recited in claim 2, 3, 4, 5, 6, or, 7 wherein the silicon hydride is R⁵ _(n) SiH_(4-n), R⁵ _(m) H_(3-m) SiOSiR⁵ _(m) H_(3-m), a cyclic siloxane of the formula (R⁵ ₂ SiO)_(x) (R⁵ _(t) H_(2-t) SiO)_(y), or a linear polysiloxane of the formula R⁵ ₃ SiO(R⁵ ₂ SiO)_(q) (R⁵ _(s) H_(2-s) SiO)_(r) SiR⁵ ₃, wherein:each R⁵ is independently alkyl containing 1 to 20 carbon atoms, aryl, chloro, bromo, alkoxy containing 1 to 4 carbon atoms, or acyloxy containing 1 to 6 carbon atoms; n is 1, 2, or 3; m is 0, 1, or
 2. x+y is 3, 4, or 5, y is an integer of one or more; t is 0 or 1; q is 0 or an integer of 1 or more; r is an integer of 1 or more; and each s is independently 0 or
 1. 9. The process as recited in claim 1 wherein the silicon hydride is R⁵ _(n) SiH_(4-n), R⁵ _(m) H_(3-m) SiOSiR⁵ _(m) H_(3-m), a cyclic siloxane of the formula (R⁵ ₂ SiO)_(x) (R⁵ _(t) H_(2-t) SiO)_(y), or a linear polysiloxane of the formula R⁵ ₃ SiO(R⁵ ₂ SiO)_(q) (R⁵ _(s) H_(2-s) SiO)_(r) SiR⁵ ₃, wherein:each R⁵ is independently alkyl containing 1 to 20 carbon atoms, aryl, chloro, bromo, alkoxy containing 1 to 4 carbon atoms, or acyloxy containing 1 to 6 carbon atoms; n is 1, 2, or 3; m is 0, 1, or
 2. x+y is 3, 4, or 5, y is an integer of one or more; t is 0 or 1; q is 0 or an integer of 1 or more; r is an integer of 1 or more; and each s is independently 0 or
 1. 10. The process as recited in claim 9 wherein each R⁵ is independently methyl, ethyl, phenyl, methoxy, ethoxy, or chloro.
 11. The process as recited in claim 9 wherein q+r is about 5 to about 10,000.
 12. The process as recited in claim 11 wherein q+r is about 10 to about 1,000.
 13. The process as recited in claim 1, 2, 3, 4, 5, 6, 7, or 9 carried out at a temperature of about 0° C. to about 200° C.
 14. The process as recited in claim 13 carried out at a temperature of about 20° C. to about 60° C.
 15. The process as recited in claim 1, 2, 3, 4, 5, 6, 7 or 9 wherein the ratio of moles of olefin to equivalents of silicon hydride is about 3:1 to about 1.3.
 16. The process as recited in claim 15 wherein said ratio is about 1.3:1 to about 1:1.
 17. The process as recited in claims 1, 2, 3, 4, 5, 6, 7 or 9 wherein the ratio of moles of cobalt catalyst to equivalents of silicon hydride is about 0.1:1 to about 0.0001:1.
 18. The process as recited in claim 17 wherein said ratio is 0.01:1 to 0.005:1. 